WO2006008914A1 - Composition pour enduit protecteur et procédé de formation du motif de l’enduit protecteur - Google Patents

Composition pour enduit protecteur et procédé de formation du motif de l’enduit protecteur Download PDF

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Publication number
WO2006008914A1
WO2006008914A1 PCT/JP2005/011737 JP2005011737W WO2006008914A1 WO 2006008914 A1 WO2006008914 A1 WO 2006008914A1 JP 2005011737 W JP2005011737 W JP 2005011737W WO 2006008914 A1 WO2006008914 A1 WO 2006008914A1
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Prior art keywords
group
resist composition
component
acid
acid generator
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PCT/JP2005/011737
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English (en)
Japanese (ja)
Inventor
Hiromitsu Tsuji
Yoshiyuki Utsumi
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Tokyo Ohka Kogyo Co., Ltd.
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Publication of WO2006008914A1 publication Critical patent/WO2006008914A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

  • Resist composition and resist pattern forming method Resist composition and resist pattern forming method
  • the present invention relates to a resist composition used in a resist pattern forming method including an immersion lithography (immersion exposure) step, and a resist pattern forming method using the resist composition.
  • a lithography method is frequently used for the production of fine structures in various electronic devices such as semiconductor devices and liquid crystal devices.
  • lithography method for example, in the most advanced region using Ar F excimer laser, it is possible to form a fine resist pattern with a line width of about 90 nm.
  • further miniaturization further miniaturization of the resist pattern is required.
  • a light source having a shorter wavelength for example, an F array is used.
  • the first, light source wavelength using EUV (extreme ultraviolet light), EB (electron beam), X-rays, etc., exposure device lens numerical aperture (NA) large aperture (high NA), etc. Is common.
  • EUV extreme ultraviolet light
  • EB electron beam
  • X-rays X-rays
  • NA numerical aperture
  • high NA high NA
  • a resist that satisfies the high sensitivity to such a short wavelength light source and the high resolution capable of reproducing a pattern with fine dimensions a base resin whose alkali solubility is changed by the action of an acid
  • a chemically amplified resist composition containing an acid generator that generates an acid upon exposure is known.
  • shortening the wavelength of the light source requires an expensive new exposure apparatus.
  • NA has a limit because NA and the depth of focus are in a trade-off relationship, and it is difficult to achieve resolution without reducing the depth of focus.
  • Immersion lithography a method called “immersion lithography” has been reported (for example, see Non-Patent Documents 1 to 3).
  • a portion between a lens, which is conventionally filled with an inert gas such as air or nitrogen, and a resist layer on the wafer is larger than the refractive index of air.
  • exposure is performed in a state filled with a solvent having a threshold refractive index, for example, pure water, a fluorine-based inert liquid, or the like.
  • a solvent having a threshold refractive index for example, pure water, a fluorine-based inert liquid, or the like.
  • Immersion lithography can be performed using an existing exposure apparatus. Therefore, Immersion Lithography is expected to be able to form resist patterns with low cost, high resolution, and excellent depth of focus, and in the manufacture of semiconductor devices that require large capital investment. In terms of cost and lithography characteristics such as resolution, the semiconductor industry is attracting a great deal of attention.
  • Non-Patent Document 1 Journal of Vacuum Science & Technology B (USA), 1999, No. 17, No. 6, pages 3306-3309.
  • Non-Patent Document 2 Journal of Vacuum Science & Technology B (USA), 2001, 19th, No. 6, 2353-2 356.
  • Non-Patent Document 3 Proceedings of SPIE (USA) 2002, 4691, 459-465.
  • a resist pattern as good as the conventional normal exposure process can be formed by immersion lithography.
  • immersion lithography 1, as described above, the solvent contacts the resist layer and the lens during exposure.
  • the resist layer changes in quality due to elution of the substances contained in the resist into the solvent, and the performance of the resist layer deteriorates, the refractive index of the solvent changes locally due to the eluted substance, or the eluted substance is found on the lens surface.
  • Contamination of the resist pattern may adversely affect the resist pattern formation. That is, problems such as deterioration of sensitivity, the resulting resist pattern T-top shape, and swelling of the resist pattern surface are expected.
  • the present invention has been made in view of the above circumstances. It is an object of the present invention to provide a resist composition that can reduce elution of a substance into a solvent used in a sography process, and a resist pattern forming method using the resist composition.
  • the first aspect of the present invention comprises a step of immersion exposure comprising a resin component (A) whose alkali solubility is changed by the action of an acid and an acid generator component (B) that generates an acid upon exposure.
  • the acid generator component (B) contains an onium salt-based acid generator (B1) represented by the following general formula (b-1). This is a resist composition.
  • R U to R 13 each independently represents an aryl group or an alkyl group, and at least one of 1 to! ⁇ 1 3 represents an aryl group in which at least one hydrogen atom is substituted with an alkyl group. Represents a group, and represents ⁇ -on. ]
  • the second aspect of the present invention includes a rosin component (A) whose alkali solubility is changed by the action of an acid, and an acid generator component (B) that generates an acid upon exposure, and is subjected to immersion exposure.
  • a resist composition used in a resist pattern forming method including the step of: wherein the acid generator component (B) contains an onium salt acid generator (B2) having a cyclic group-containing anion.
  • the resist composition characterized by the above.
  • the third aspect of the present invention is the resist composition of the first aspect or the second aspect.
  • the resist composition and the resist pattern forming method of the present invention can reduce substance elution into a solvent (hereinafter sometimes referred to as an immersion medium) used in an immersion lithography process.
  • a solvent hereinafter sometimes referred to as an immersion medium
  • the resist composition according to the first aspect of the present invention comprises a resin component (A) whose alkali solubility is changed by the action of an acid (hereinafter sometimes referred to as component (A)) and an acid that generates an acid upon exposure.
  • Generator component (B) (hereinafter sometimes referred to as component (B)), and used in a resist pattern forming method including a step of immersion exposure, wherein the component (B) It contains an onium salt acid generator (B1) represented by the formula (b 1).
  • R U to R 13 each independently represents an aryl group or an alkyl group, and at least one of R n to R 13 has at least one hydrogen atom substituted with an alkyl group. It must be an aryl group.
  • Examples thereof include phenyl groups and naphthyl groups, and aryl groups having 6 to 10 carbon atoms are preferred because they can be synthesized at low cost
  • alkyl groups of R U to R 13 are particularly limited.
  • Examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, etc. From the viewpoint of excellent resolution, it is preferably 1 to 5 carbon atoms.
  • Methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, n pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nor group A decanyl group, etc. can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
  • all R U to R 2 or more of the 13 it is preferably a ⁇ aryl group instrument R U to R 13 rather more preferably a Ariru group, R U to R 13 Most preferred are all phenolic groups.
  • alkyl group in the “aryl group in which at least one hydrogen atom is substituted with an alkyl group” is not particularly limited, and for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Groups and the like. Of these, a branched alkyl group having 10 or less carbon atoms is preferred, and a branched alkyl group having 5 or less carbon atoms is more preferred, and a tertiary alkyl group is particularly preferred because of excellent effects of the present invention. Specific examples include a tert butyl group.
  • salt-based acid generator (B1) include bis- (4 tert butylphenol) chloromethane sulfonate or nonafluorobutane sulfonate. Salt; tri (4 methylphenol) sulfurium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, (4 methylphenol) diphenylsulfonate Trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, tri (4-tert-butyl) phenylsulfotrifluoromethanesulfonate, heptafluoro Examples thereof include sulfopropane salts such as lopropane sulfonate and nonafluorobutane sulfonate thereof.
  • an acid salt-based acid generator (B1) force includes an acid salt-based acid generator (B11) represented by the following general formula (b-2).
  • the effect of the present invention is excellent and preferable.
  • R M to R lb each independently represents an alkyl group, and p, q and r each independently represents an integer of 1 to 5 and represents ⁇ -on. ]
  • examples of the alkyl group of R 14 to R 16 include the same alkyl groups as those in the above “aryl group in which at least one hydrogen atom is substituted with an alkyl group”.
  • . p, q, and r each independently represent an integer of 1 to 5, more preferably an integer of 1 to 3, and most preferably 1.
  • the Z-on is not particularly limited, and any Z-on that has been proposed as a key-on in a known acid generator used in a conventional chemically amplified resist composition. It may be.
  • Z is a fluorinated alkyl sulfonate ion in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom.
  • a perfluoroalkylsulfonic acid ion in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is preferred.
  • the form salt-based acid generator (B11) is excellent in the effect of the present invention because the elution amount of the cation portion into the immersion medium is particularly small. Therefore, the following general formula (b-3) It is preferable that the acid salt type acid generator (B12) represented by these is included.
  • s represents an integer of 1 to 10.
  • s is preferably an integer of 1 to 8, more preferably an integer of 1 to 4.
  • the form salt acid generator (B1) may be used alone or in combination of two or more.
  • the component (B) is further used in the onion salt-based acid generator (B2) shown in the second embodiment to be described later or a conventional chemically amplified resist composition.
  • it may contain a known acid generator (hereinafter sometimes referred to as other acid generator (B3))
  • the proportion of the salt salt acid generator (B1) in the component (B) If the salt salt acid generator (B2) is not included, it is preferable that the total amount of component (B) is 25 to: LOO% by mass, and 50 to 100% by mass is more preferable. ⁇ : More preferably LOO mass%, most preferably 100 mass%.
  • the effect of the present invention is sufficient when the proportion of the salt salt acid generator (B1) in the component (B) is 25% by mass or more.
  • the component (B) contains both the onion salt acid generator (B1) and the onion salt acid generator (B2)
  • the onion salt acid generator (B1) and the onion salt generator It is preferable that the total amount of the acid generator (B2) is 25 to 100% by mass of the total component (B). 30 to: LOO% by mass is more preferable.
  • the ratio of the sodium salt-based acid generator (B1) to the sodium salt-based acid generator (B2) is not particularly limited, but considering the suppression of elution into the immersion medium, 1 : 9-9: 1 is preferred 8: 2-2: 8 is more preferred
  • sodium salt acid generators such as odonium salts and sulfo salt, oxime sulfonate acid generators, bisalkyl or bisaryl sulfone have been used.
  • -Diazomethane acid generators such as diazomethanes and poly (bissulfo-) diazomethanes, nitrobenzil sulfonate acid generators, iminosulfonate acid generators, disulfone acid generators, etc.
  • Specific examples of the acid salt-based acid generator in the other acid generator (B3) include diphenylo trifluoromethanesulfonate, nonafluorobutane sulfonate, and triphenol-noresnorephonium.
  • oxime sulfonate-based acid generator examples include ⁇ - ( ⁇ -toluenesulfooxyoximino) -benzyl cyanide, ⁇ - ( ⁇ -chlorobenzenesulfo-oxyoximino) -benzil cyanide, a- (4-Trobenzenesulfo-luximino) -benzyl cyanide, ⁇ - (4-nitro-2-trifluoromethylbenzenesulfo-roximino) -benzyl cyanide, a- (benzenesulfo-roximino) -4-chloro Oral bendyl cyanide, a-(benzenesulfoloxymino)-2, 4-dichlorobenzil cyanide, ⁇ -(benzenesulfooxyximino)-2, 6 -dichlorobenzil cyanide, ⁇ -(benzene Sulfo-Luoxyimino) -4
  • bisalkyl or bis (arylsulfol) diazomethanes include bis (isopropylsulfol) diazomethane, bis ( ⁇ toluenesulfol) diazomethane, and bis (1,1- Examples thereof include dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, and bis (2,4 dimethylphenylsulfonyl) diazomethane.
  • Poly (bissulfonyl) diazomethanes include, for example, 1,3 bis (phenylsulfodiazomethylsulfo) propane (composite compound, decomposition point 135 ° C) having the following structure, 1,4 bis (phenylsulfodiazomethylsulfol) butane (Compound B, decomposition point 147 ° C), 1,6 bis (phenylsulfodidiazomethylsulfol) hexane Compound C, melting point 132 ° C, decomposition point 145 ° C), 1,10 bis (phenolsulfo-diazomethylsulfo) decane (Compound D, decomposition point 14 7 ° C), 1, 2 bis (cyclohexylsulfoldiazomethylsulfol) ethane (compound E, decomposition point 149 ° C), 1,3 bis (cyclohexylsulfoldiazomethylsulfol) propane (Compound F,
  • the content of the component (B) is more preferably 1 to 10 parts by mass, preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the component (A). If it is less than the above range, pattern formation may not be sufficiently performed, and if it exceeds the above range, it is difficult to obtain a uniform solution and storage stability is lowered. This may cause
  • the component (A) is not particularly limited, and may be one or more alkali-soluble resins or alkali-soluble resins that have been proposed as base resins for chemically amplified resists. Coffin can be used.
  • the former is a so-called negative type resist composition, and the latter is a so-called positive type resist composition.
  • a crosslinking agent is blended in the resist composition together with the alkali-soluble resin and the component (B).
  • a strong acid acts to cause cross-linking between the alkali-soluble resin and the cross-linking agent, thereby changing to alkali-insoluble.
  • alkali-soluble resin examples include ⁇ (hydroxyalkyl) acrylic acid, or ⁇ -
  • (Hydroxyalkyl) Lower alkyl ester power of acrylic acid A resin having a unit derived from at least one selected is preferable because it can form a good resist pattern with little swelling in immersion exposure.
  • the crosslinking agent for example, an amino crosslinking agent that is hardly soluble in a solvent for immersion exposure such as glycoluryl having a methylol group or an alkoxymethyl group, particularly a butoxymethyl group is usually used. In immersion exposure, a favorable resist pattern with less swelling can be formed, which is preferable.
  • the amount of the crosslinking agent is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the component ( ⁇ ) is an alkali-insoluble one having a so-called acid dissociable, dissolution inhibiting group, and when an acid is generated from the component ( ⁇ ) upon exposure, a strong acid is converted into the acid. Dissociation By dissociating the dissolution inhibiting group, the component (ii) becomes alkali-soluble. Therefore, when the resist composition is selectively exposed to the resist composition applied on the substrate while forming the resist pattern, the alkali solubility of the exposed portion is increased and alkali development can be performed.
  • the component (ii) preferably contains a structural unit from which a (a lower alkyl) acrylate ester is also derived in both cases of positive and negative types.
  • structural unit means a monomer unit (monomer unit) constituting a polymer.
  • (a lower alkyl) acrylate ester” means one or both of an acrylate ester and an ⁇ - lower alkyl acrylate ester such as a methacrylic ester.
  • the lower alkyl group as the substituent at the 1-position of “( ⁇ lower alkyl) acrylate ester” is an alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, Examples thereof include lower linear or branched alkyl groups such as propyl group, isopropyl group, n butyl group, isobutyl group, tert butyl group, pentyl group, isopentyl group and neopentyl group.
  • the - "(a lower alkyl) acrylate Esuteruka ⁇ et the induced structural unit” refers to a structural unit formed by (alpha-lower alkyl) cleavage of the ethylenic double bond of an acrylate ester.
  • the component ( ⁇ ) contains a structural unit derived from —lower alkyl) acrylate ester, preferably at least 20 mol%, more preferably at least 50 mol%. Is desirable.
  • the component (A) has a structural unit (al) derived from an acrylate ester group having an acid dissociable, dissolution inhibiting group (ex lower alkyl). Is preferred.
  • the acid dissociable, dissolution inhibiting group in the structural unit (al) has an alkali dissolution inhibiting property that makes the whole component (A) insoluble in alkali before exposure, and (B) the action of an acid that also generated component power after exposure. It can be used without particular limitation as long as it can be dissociated by (1) to change the entire component (A) into alkali-soluble.
  • (meth) acrylic acid and a group forming a cyclic or chain tertiary alkyl ester, a tertiary alkoxy carbo yl group, or a chain alkoxyalkyl group are widely known. Talk to you.
  • the term “(meth) acrylic acid ester” means either an acrylic acid ester or a methacrylic acid ester.
  • an acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group can be preferably used.
  • the term “aliphatic” in the present invention is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
  • the term “aliphatic cyclic group” means a monocyclic group or a polycyclic group (alicyclic group) having no aromaticity, and in this case, the “aliphatic cyclic group” means carbon and The group is not limited to a group consisting of hydrogen (hydrocarbon group), but is preferably a hydrocarbon group.
  • the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
  • a polycyclic group (alicyclic group) is preferred.
  • Such aliphatic cyclic groups include, for example, a monocycloalkane, bicycloalkane, tricycloalkane, teracycloalkane, etc. which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Examples include a group excluding a hydrogen atom.
  • monocycloalkanes such as cyclopentane and cyclohexane
  • groups obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • Such monocyclic or polycyclic groups can be used by appropriately selecting the intermediate forces proposed in the ArF resist.
  • a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a tetracyclododecanyl group are preferred, and an adamantyl group is particularly preferred.
  • structural unit (al) include structural units represented by the following general formulas (al-1) to (al-9).
  • R is a hydrogen atom or a-lower alkyl group, and R 2 and R 3 are each independently a lower alkyl group.
  • R is a hydrogen atom or an ⁇ -lower alkyl group, and R 4 is a tertiary alkyl group.
  • R is a hydrogen atom or an ⁇ -lower alkyl group.
  • R is a hydrogen atom or an ⁇ -lower alkyl group, and R 5 is a methyl group.
  • R is a hydrogen atom or an ⁇ -lower alkyl group, R. is a lower alkyl group.
  • R is a hydrogen atom or an ⁇ -lower alkyl group.
  • R is a hydrogen atom or an ⁇ lower alkyl group
  • R 7 is a lower alkyl group.
  • Each of the above and R 6 to R 7 is a lower straight chain or branched chain having 1 to 5 carbon atoms.
  • Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
  • a methyl group or an ethyl group is preferable.
  • R 4 is a tertiary alkyl group such as a tert-butyl group or a tert-amyl group, and a tert-butyl group is industrially preferred.
  • the structural unit (al) one type may be used alone, or two or more types may be used in combination. Also good. (A) the amount of the structural units in the component (al) is, (A) and against the total of all the structural units of the component, 5 to 60 mole 0/0 force S Preferably, 5 to 50 mole 0/0 Gayori preferable. By setting it to the lower limit value or more, a pattern can be obtained when the resist composition is used, and by setting it to the upper limit value or less, it is possible to balance with other structural units.
  • the component (A) has, in addition to the structural unit (al), a structural unit (a2) derived from an (a-lower alkyl) acrylate ester having a latathone-containing monocyclic or polycyclic group. I like it.
  • the lathetone-containing monocyclic or polycyclic group of the structural unit (a2) is used to increase the adhesion of the resist film to the substrate or to improve the hydrophilicity with the developer when the component (A) is used for forming a photoresist film. It is effective in improving the sex.
  • the rataton here refers to one ring containing the O—C (O) — structure, and this is counted as the first ring. Therefore, a monocyclic group in the case of only a rataton ring, and a polycyclic group in the case of having another ring structure, regardless of the structure.
  • any unit can be used without particular limitation as long as it has both such a structure of latatane (-O-C (O)-) and a cyclic group.
  • the latatatone-containing monocyclic group includes a group in which y petit-mouth rataton force hydrogen atom is removed
  • the latatone-containing polycyclic group includes a bicycloalkane having a latathone ring.
  • tricycloalkane and tetracycloalkane forces also include groups in which one hydrogen atom has been removed.
  • a group obtained by removing one hydrogen atom from a latathone-containing tricycloalkane having the following structural formula (IV) or structural formula (V) is advantageous in terms of industrial availability.
  • Examples of the structural unit (a2) include structural units derived from acrylate esters containing a ratatone-containing monocycloalkyl group or tricycloalkyl group ( ⁇ -lower alkyl group), etc. Is mentioned. More specifically, examples of the structural unit (a2) include structural units represented by general formula (a2 a2-5) shown below.
  • R ′ is a hydrogen atom or a lower alkyl group.
  • R ′ is a hydrogen atom or a lower alkyl group.
  • R ′ is a hydrogen atom or a lower alkyl group
  • R 8 and R 9 are each independently a hydrogen atom or a lower alkyl group.
  • R ′ is a hydrogen atom or a lower alkyl group, and o is 0 or 1.
  • R ′ is a hydrogen atom or a lower alkyl group
  • the lower alkyl group for R ′ is the same as the lower alkyl group for R in the structural unit (al).
  • R 8 and R 9 are each independently a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. Atom is preferred.
  • ⁇ -butyrolatatone ester of acrylic acid (general formula (a2-3) having an ester bond to the ex carbon on the Lataton skeleton), ie, ( ⁇ -lower alkyl) acrylic of ⁇ -butyrolataton
  • a structural unit that also induces acid ester power is preferred.
  • it is derived from norbornan lactone ester of (a lower alkyl) acrylic acid represented by general formula (a2-1) or (a2-2), that is, (lower alkyl) acrylic acid ester ester of norbornane ratataton.
  • the structural unit is preferable because the shape of the resist pattern obtained when used in a resist composition, for example, rectangularity is even better.
  • the structural unit represented by the general formula (a2-2) is preferable because its effect is extremely high. Of these, the structural unit represented by the general formula (a2-3) is most preferred.
  • the component (A) as the structural unit (a2), only one type may be used, or two or more types different from each other may be used in combination. It is preferable to introduce two or more kinds of different rataton skeletons into the skeleton of the component (A), because the adhesion of the photoresist film to the substrate further improves the affinity with the alkaline developer and the etching resistance.
  • the proportion of the structural unit (a2) is preferably 5 to 80 mol%, more preferably 5 to 60 mol%, based on the total of all the structural units constituting the component (A). By setting it to the lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to balance with other structural units.
  • the component (A) further contains a polar group-containing aliphatic hydrocarbon group ( ⁇ lower alkyl) talyl. Acid ester power It is preferred to have a derived structural unit.
  • the hydrophilicity of the component (A) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is improved, and the resolution is improved.
  • the polar group include a hydroxyl group and a cyano group, and a hydroxyl group is particularly preferable.
  • the aliphatic hydrocarbon group include a linear or branched hydrocarbon group (alkylene group) having 1 to 10 carbon atoms and a polycyclic aliphatic hydrocarbon group (polycyclic group).
  • the polycyclic group include For example, many resins have been proposed for resist compositions for ArF excimer lasers, and the intermediate force of these can be selected and used as appropriate.
  • a structural unit containing a hydroxyl group, a cyano group or a carboxyl group-containing aliphatic polycyclic group and derived from a (meth) acrylic acid ester is more preferable.
  • the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, or the like. Specifically, adamanta
  • Groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as benzene, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • a polycycloalkane such as benzene, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • Many such polycyclic groups have been proposed in polymers (resin components) for resist compositions for ArF excimer lasers, and can be appropriately selected from those used.
  • an adamantyl group, norbornyl group, and tetracyclododecanyl group are preferred industrially.
  • the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, -lower alkyl) talyl
  • a structural unit derived from a hydroxyethyl ester of an acid is preferred.
  • the hydrocarbon group is a polycyclic group, structural units represented by the following formulas (a3 ⁇ l) and (a3 ⁇ 2) It is mentioned as preferable.
  • R ′ is the same as above, and n is an integer of 1 to 3.
  • n is 1, and a force in which the hydroxyl group is bonded to the 3-position of the adamantyl group S is preferable.
  • R ′ is the same as defined above, and k is an integer of 1 to 3.
  • the structural unit (a3) is not an essential component of the component (A)! /, But when it is contained in the component (A), it is based on the total of all structural units constituting the component (A). Te, from 5 to 50 mole 0/0, and preferably contain 1 0-40 mol% preferred. By setting it above the lower limit, the effect of improving LER (Line Edge Roughness) is improved. If the upper limit is exceeded, the resist pattern shape may deteriorate due to the balance of other structural units.
  • Component (A) is within the range not impairing the effects of the present invention, other structural units (a4) not classified into the above structural units (al) to (a3), that is, acid dissociable, dissolution inhibiting groups, latathone functional groups, You may have the structural unit which does not contain a polar group.
  • the structural unit (a4) for example, a structural unit containing an acid non-dissociable aliphatic polycyclic group and derived from ( ⁇ -lower alkyl) acrylic acid ester is preferable.
  • an isolated pattern force semi-dense pattern (a line-and-space pattern having a space width of 1.2 to 2 with respect to a line width of 1). Excellent resolution and preferable.
  • Examples of the polycyclic group include those similar to those exemplified in the case of the structural unit (a3), and are conventionally known as ArF positive resist materials! It can be used by appropriately selecting from a large number. In particular, at least one selected from tricyclodecanyl group, adamantyl group, tetracyclododecyl group, and isobornyl group It is preferable in terms of easy availability. In particular, the following general formulas (a4-1) to (a4-3) are preferable.
  • Powerful structural unit (a4) is not an essential component of component (A)! /, But when it is included in component (A), all structural units constituting component (A) the total of the structural unit (a4) from 1 to 30 mol 0/0, and preferably to 10 to 20 mole 0/0 contained, isolated pattern mosquitoes in resolution of Semidensupata Ichin per cent, Te good Because improvement effect is obtained, it is preferable.
  • the mass average molecular weight of the component (A) (in terms of polystyrene, the same shall apply hereinafter) is particularly limited. , Force 2000 ⁇ 30000 force is preferable, moth type is more preferable than 2000 ⁇ 20000 force, 4000 ⁇ 15000 force S more preferable, positive type is more than 5000 ⁇ 30000 force S more preferable 8000 ⁇ 20000 force Further preferred. If it is larger than this range, the solubility in the resist solvent will be poor, and if it is small, the dry etching resistance and resist pattern cross-sectional shape may be deteriorated.
  • the resin component or the component (A) and the component (B) and any of the components (D) and Z or (E) described later are combined with an organic solvent (C) ( Hereinafter, it may be dissolved in (C) component).
  • organic solvent (C) hereinafter, it may be dissolved in (C) component.
  • any component can be used as long as it can dissolve each component used to form a uniform solution.
  • two or more types can be appropriately selected and used.
  • ketones such as ⁇ -butyrolatatone, acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone (HP), ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate , Polyhydric alcohols such as propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof Cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl Methyl Kishipuropion acid, ethoxy
  • esters such as ethyl propionate
  • a mixed solvent in which propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent are mixed is preferable.
  • the mixing ratio may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8. It is preferable to be within the range. More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 8: 2 to 2: 8, more preferably 7: 3 to 3: 7.
  • the organic solvent a mixed solvent of at least one selected from PGMEA and EL and ⁇ -petit-mouth rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • the amount of component (C) used is not particularly limited, and is a concentration that can be applied to a support such as a substrate and is appropriately set according to the coating film thickness. It is used so that the solid content concentration of the composition is in the range of 2 to 20% by mass, preferably 5 to 15% by mass.
  • Component (D) In the positive resist composition of the present invention, the resist pattern shape and placement? ) In order to improve post exposure stability of the latent image formed by tne pattern-wise exposure of the resist layer (PED: post exposure delay), etc. Compound (D) (hereinafter referred to as component (D)) can be added. Since a wide variety of components (D) have already been proposed, any known one may be used. Amines, particularly secondary lower aliphatic amines, are used as tertiary lower aliphatic amines. preferable.
  • the lower aliphatic amine refers to an alkyl or alkyl alcohol amine having 12 or less carbon atoms
  • examples of the secondary and tertiary amines include trimethylamine, jetylamine, triethylamine, di-n. -Propylamine, tri-n-propylamine, tri-n-pentylamine, tri-n-dodecylamine, tri-n-octylamine, diethanolamine, triethanolamine, triisopropanol and the like.
  • an aliphatic tertiary amine having an alkyl group having 5 to 12 carbon atoms is preferred, and tri-n-octylamine is particularly preferred.
  • a nitrogen-containing organic compound represented by the following general formula (VI) can also be preferably used. [0082] [Chemical 25]
  • R 11 R 12 each independently represents a lower alkylene group, and R 13 represents a lower alkyl group.
  • scale 11, R 12, R 13 is a linear, branched, may be cyclic, it is preferably straight-chain, branched.
  • Carbon numbers of 1 , R 12 and R 13 are each 1 to 5, preferably 1 to 3, from the viewpoint of molecular weight adjustment.
  • the carbon numbers of the scale 11 , R 12 and R 13 may be the same or different.
  • 1 and R 12 may have the same structure or different structures.
  • Examples of the compound represented by the general formula (VI) include tris- (2-methoxymethoxyethyl) amine, tris-1- (2-methoxy (ethoxy)) ethylamine, and tris- (2- (2-methoxyethoxy). ) Methoxyethyl) amine.
  • tris-2- (2-methoxy (ethoxy)) ethylamine is preferred.
  • the compound represented by the above general formula (VI) is particularly preferable, and tris-2- (2-methoxy (ethoxy)) ethylamine is particularly preferable because of its low solubility in the immersion medium. .
  • These may be used alone or in combination of two or more.
  • These components (D) are usually used in the range of 0.01 to 5.0% by mass with respect to component (A).
  • the component (D) and the component (E) can be used in combination, or one kind of force can be used.
  • organic carboxylic acid for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Phosphorus oxalic acid or its derivatives include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other derivatives such as phosphoric acid, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid -Di-n-butyle Derivatives like phosphonic acids and their esters such as stealth, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, phosphinic acids such as phosphinic acid, phenylphosphinic acid and derivatives such as their esters Among these, phosphonic acid is particularly preferable.
  • Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • the positive resist composition of the present invention further contains miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and a dissolution agent.
  • miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and a dissolution agent.
  • An inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, and the like can be added as appropriate.
  • the above-described components are treated by a conventional method.
  • Mixing and stirring with the above, and if necessary, it may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three-roll mill. Further, after mixing, the mixture may be filtered using a cocoon mesh or a membrane filter.
  • the resist composition according to the second aspect of the present invention is characterized in that the component (B) contains an acid salt-based acid generator (B2) having a cyclic group-containing ion. Is the same as the resist composition of the first embodiment.
  • a cyclic group-containing cation means that the ionic strength of the form salt acid generator contains a cyclic group in its structure.
  • a 3- to 20-membered ring (the number of atoms constituting the basic ring excluding the substituent is 3 to 20) is preferable in terms of the effect of the present invention, which may be monocyclic or polycyclic.
  • a 3- to 15-membered ring is more preferred, and a 5- to 12-membered ring is most preferred.
  • the basic ring may be a heterocyclic group containing a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, or may be a hydrocarbon group composed solely of carbon atoms and hydrogen atoms.
  • the basic ring may have a sulfol group (one SO—), a carboxy group (one CO—), etc.
  • an aliphatic group that is aliphatic or aromatic is more preferable.
  • a monocyclic ring that has been conventionally known as an ArF positive resist material is more preferable.
  • a polycyclic aliphatic hydrocarbon group can be used, and a monocyclic group such as a group obtained by removing one or two hydrogen atoms from a monocycloalkane such as cyclohexane or cyclopentane; Polycyclic alkanes such as cycloalkanes, tetracycloalkanes, and other polycyclic alkanes in which one or two hydrogen atoms are removed, such as adamantane, norbornane, isobornane, tricyclodecane, tetra Examples of polycycloalkane forces such as cyclododecane include groups in which one or two hydrogen atoms have been removed.
  • a substituent having no charge such as an alkyl group may be bonded to the basic ring, but for the effect of the present invention, the shorter the substituent length, the better. Most preferably, the smaller the number of carbon atoms in the alkyl group, the less the preferred substituents, for example, those having 5 or less carbon atoms.
  • the cyclic group-containing cation may have a negatively charged group or atom (for example, N) on the basic ring of these cyclic groups.
  • a group having a negative charge (for example, SO-) or an atom may be bonded to the cyclic group.
  • the onion salt-based acid generator (B2) strength includes the compound (B21) represented by the following general formula (b-4) because the effects of the present invention are excellent.
  • X represents a C 2-6 alkylene group in which at least one hydrogen atom is substituted with a fluorine atom;
  • R 21 to R 23 each independently represents an aryl group or an alkyl group; , At least one of R 21 to R 23 represents an aryl group]
  • X represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group preferably has 2 carbon atoms. -6, more preferably 3-5, most preferably 3.
  • the smaller the number of carbon atoms in the alkylene group of X the better the solubility in a resist solvent is, and it is preferable.
  • the alkylene group of X as the number of hydrogen atoms substituted with fluorine atoms increases, the strength of the acid increases. In addition, it is preferable because it improves transparency to high-energy light and electron beams of 200 nm or less.
  • the proportion of fluorine atoms in the alkylene group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably 100%, that is, all hydrogen atoms are replaced with fluorine atoms.
  • Perfluoroalkylene group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably 100%, that is, all hydrogen atoms are replaced with fluorine atoms.
  • R 21 ⁇ R 23 each independently represent a Ariru group or an alkyl group. Further, at least one of R 21 to R 23 represents an aryl group. Of R 21 to R 23, all 2 or more is a Ariru group this and is preferred instrument R 21 to R 23 is most preferably a Ariru group.
  • the aryl group of R 21 to R 23 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, which may or may not be substituted with an alkyl group, a halogen atom, or the like. Group and naphthyl group. Aryl groups having 6 to 10 carbon atoms are preferred because they can be synthesized at low cost.
  • the alkyl group for R 21 to R 23 is not particularly limited, and examples thereof include straight chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, de-force- Group, etc., excellent resolution
  • a methyl group is preferable because it can be synthesized at a low cost. Among these, it is most preferable that all of R 21 to R 23 are a phenol group.
  • Compound (B21) may be used alone or in combination of two or more.
  • R 24 to R 26 each independently represents an aryl group or an alkyl group, and at least one of R 24 to R 26 represents an aryl group
  • Y represents a cyclic group, and examples of the cyclic group include the same groups as described above. .
  • Y is preferably an aliphatic hydrocarbon group from the viewpoint of excellent effects of the present invention, and in particular, Y is more preferably an adamantyl group.
  • R 24 to R 26 are the same as R 21 to R 23 in the above formula (b-4).
  • Compound (B22) may be used alone or in combination of two or more!
  • an onium salt-based acid generator (B2) force It is preferable that one or both of the above compounds (B21) and (B2 2) are included.
  • O - ⁇ beam salt-based acid generator in (B2) the total amount of the compound (B21) and (B22) are O - ⁇ beam salt acid generating agent (B2) 50 ⁇ : LOO mass 0/0 good 80 ⁇ : LOO% by mass is more preferred, most preferably 100% by mass, that is, an onium salt-based acid generator (B2) force It is preferable to consist only of compound (B21) and Z or (B22) .
  • the ratio of the compounds (B21) and (B22) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the component (B) further includes an onium salt acid generator (B1) shown in the first embodiment and a known acid used in conventional chemically amplified resist compositions. It may contain a generator (other acid generator (B3)), but the proportion of the acid salt acid generator (B2) in the component (B) When the agent (B1) is not included, it is preferable that the total amount of the component (B) is 25 to: LOO mass%. 30 to LOO mass% is more preferable. (B) The effect of the present invention is sufficient when the proportion of the salt salt acid generator (B1) in the component is 25% by mass or more.
  • the onion salt acid generator (B1) in the component (B) contains both the onion salt acid generator (B1) and the onium salt acid generator (B2)
  • the onion salt acid generator (B1) in the component (B) contains the onion salt acid generator (B1) in the component (B)
  • the total amount of the acid salt acid generator (B2) and the ratio of the acid salt acid generator (B1) and the acid salt acid generator (B2) are the same as in the first embodiment. It is the same as described.
  • a resist pattern forming method useful for the present invention will be described.
  • a resist composition according to the present invention is applied onto a substrate such as a silicon wafer with a spinner or the like, and then pre-beta (PAB treatment) is performed.
  • PAB treatment pre-beta
  • cash register A two-layer laminate in which an organic antireflection film is provided on the coating layer of the strike composition may be used, and a three-layer laminate in which a lower antireflection film is provided thereon.
  • the process so far can be performed using a known method.
  • the operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the resist composition to be used.
  • immersion exposure Liquid Immersion Lithography
  • the space between the resist layer and the lens at the lowest position of the exposure apparatus is previously filled with a solvent having a refractive index larger than that of air. It is preferable to perform the exposure in a state filled with a solvent having a refractive index smaller than that of.
  • the wavelength used for exposure is not particularly limited. ArF excimer laser, KrF excimer laser, F laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet),
  • the resist composition according to the present invention is effective for KrF or ArF excimer lasers, particularly ArF excimer lasers.
  • the resist layer and the lens at the lowest position of the exposure apparatus are filled with a solvent larger than the refractive index of air during exposure.
  • the solvent having a refractive index larger than that of air include water and a fluorine-based inert liquid.
  • fluorinated inert liquid examples include C HC1 F, C F OCH, C F OC H,
  • the boiling point is preferably 70 to 180 ° C, more preferably 80 to 160 ° C.
  • Specific examples of the perfluorinated alkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound. More specifically, examples of the perfluoroalkyl ether compound include perfluoro mouth (2-butyl-tetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include: And perfluorotributylamine (boiling point 174 ° C).
  • fluorinated inert liquids those having a boiling point in the above range are preferable because the immersion medium can be removed after exposure by a simple method.
  • the immersion medium is preferably water because the resist composition of the present invention is particularly sensitive to water and is excellent in sensitivity and resist pattern profile shape. Water is also preferred from the viewpoint of cost, safety, environmental issues and versatility.
  • PEB post-exposure heating
  • development is performed using an alkaline developer that is an alkaline aqueous solution.
  • water rinsing is performed using pure water.
  • water is dropped or sprayed on the surface of the substrate while rotating the substrate to wash away the developer on the substrate and the resist composition dissolved by the developer. Then, by drying, a resist pattern in which the coating film of the resist composition is patterned into a shape corresponding to the mask pattern is obtained.
  • the immersion medium is used in the immersion medium used in the immersion lithography process. Elution of substances into the can be reduced. Therefore, contamination of the immersion medium is reduced, thereby reducing changes in the properties of the immersion medium, for example local changes in the refractive index. Further, contamination of the lens of the exposure apparatus is reduced. Furthermore, since the elution of the component (B) is reduced and the change in the resist composition is reduced, it is presumed that the change in the performance of the resist layer is also suppressed. For this reason, it is expected that degradation of the resolution and shape of the resist pattern to be formed can be suppressed. In addition, since contamination of the immersion medium and the lens of the exposure apparatus is reduced, it is expected to contribute to the simplification of the process and the exposure apparatus without taking protective measures against them.
  • component (A), component (B), and component (D) were uniformly dissolved in component (C) to prepare positive resist composition 1.
  • component (A) 100 parts by mass of a methacrylic acid ester / acrylic acid ester copolymer composed of three kinds of structural units represented by the following formula (1) was used.
  • the prepared component (A) had a weight average molecular weight of 10,000.
  • component (B) 11.7 parts by mass of TTBPS-PFBS was used.
  • component (C) 1250 parts by mass of propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PM”) was used.
  • component (D) 1.0 part by mass of tri-n-octylamine was used.
  • a resist pattern was formed using the positive resist composition 1 obtained above.
  • a positive resist yarn composition 1 is applied to silicon having a diameter of 8 inches using a spinner.
  • the resist layer with a film thickness of 200 nm was formed by coating on a wafer, pre-betaning on a hot plate at 130 ° C for 90 seconds, and drying.
  • a resist layer is formed in the same manner as described above, and open frame exposure is performed with an ArF excimer laser (193 nm) at an exposure amount of 30 mjZcm 2 using a simple exposure apparatus VUVES4500 (manufactured by RISOTEC Japan) (Exposure without passing through a mask) was performed.
  • VUVES4500 manufactured by RISOTEC Japan
  • an in-circle extraction tool having a diameter of 130 mm was provided on the exposed resist layer, and then 3 OmL of 23 ° C pure water was dropped and left at room temperature for 5 minutes.
  • the pure water was analyzed with CEZMS (capillary electrophoresis Z mass spectrometer) (G1600AZ manufactured by Agilent Technologies, Inc.
  • a positive resist composition was prepared in the same manner as in Example 1 except that 9.0 parts by mass of TPS-PFBS was used as the component (B) in Example 1, and the same evaluation was performed. The results are shown in Table 1.
  • Example 1 a positive resist composition was prepared in the same manner as in Example 1 except that 8.4 parts by mass of TPS—IMIDO was used as the component (B). +) And the anion part (PAG-) were measured in the same manner as in Example 1 except that the elution amount (mol Zcm 2 ) per square centimeter of the resist layer after exposure was determined. I went. The results are shown in Table 2.
  • EL lactic acid ethyl
  • PM 4: 6 (mass ratio)
  • a positive resist composition was prepared in the same manner as in Example 1 except that 1250 parts by mass of the solvent was used, and the concentrations of the component (B) in the cation part (PAG +) and the anion part (PAG-) were measured.
  • the same evaluation as in Example 1 was performed, except that the elution amount (mole Zcm 2 ) per square centimeter after exposure was determined. The results are shown in Table 2.
  • Example 2 In Example 1, except that 6.6 parts by mass of TPS-PFMS was used as the component (B), a positive resist composition was prepared in the same manner as in Example 1, and the cation part (PAG +) of the component (B) In addition, the same evaluation as in Example 1 was performed, except that the concentration of each of the light-on part (PAG—) was measured and the amount of elution (mol Zcm 2 ) per square centimeter of the resist layer after exposure was determined. It was. The results are shown in Table 2.
  • Example 1 a positive resist composition was prepared in the same manner as in Example 1 except that 12.2 parts by mass of TPS-PFOS was used as the component (B), and the cation part (PAG + ) And the key-on part (PAG-) were measured in the same manner as in Example 1 except that the elution amount (mole Zcm 2 ) per square centimeter of the resist layer after exposure was determined. It was. The results are shown in Table 2.
  • a positive resist composition was prepared in the same manner as in Example 1 except that 9.0 parts by mass of TPS-PFBS was used as the component (B) in Example 1, and the cation part (PAG +) of the component (B) Oh
  • the same evaluation as in Example 1 was performed except that the concentration of each of the light-on part (PAG-) was measured and the amount of elution (mole Zcm 2 ) per square centimeter of the resist layer after exposure was obtained. .
  • the results are shown in Table 2.
  • the resist composition of Example 1 using TTBPS-PFBS corresponding to the sodium salt acid generator (B1) was the resist composition of Comparative Example 1. Compared with the product, elution of the cation (PAG +) was almost impossible.
  • the cation (PAG +) Both the ON part (PAG-) and the pre-exposure and post-exposure powers were low.
  • both the cation part (PAG +) and the key-on part (PAG-) were eluted.
  • Examples 2 and 3 are compared with Comparative Examples 2 to 4, the resist yarns and the composites of Examples 2 and 3 are exposed to light even though the structure of the cation portion (PAG +) is the same.
  • the amount of elution of the previous cation part (PAG +) was small.
  • the amount of elution before exposure is for evaluating the amount of elution in the unexposed area when selective exposure is performed to form a resist pattern.
  • the amount of elution after exposure is evaluated for the amount of elution in the exposed area. Is for.
  • the resist composition of Examples 1 to 3 has a small amount of elution of component (C) with respect to the immersion medium (water) both before and after exposure. It is clear that the product can be suitably used for a resist pattern forming method including a step of immersion exposure.
  • Example 1 3.5 parts by mass of TPS-IMIDO as component (B), 0.6 parts by mass of tri-n-octylamine as component (D), PGMEA and propylene glycol monomethyl ether (PGME) as organic solvents
  • a positive resist composition was prepared in the same manner as in Example 1 except that 1250 parts by mass of the mixed solvent (mass ratio 6: 4) was used, and the cation part (PAG +) and the anion part of the component (B) (PAG-) Each concentration was measured, and the same evaluation as in Example 1 was performed except that the elution amount (mole Zcm 2 ) per square centimeter of the resist layer after exposure was determined. The results are shown in Table 3.
  • Example 1 a mixture of 3.5 parts by mass of TPS-PFBS as component (B) and 1.0 part by mass of MTPS-PFMS, and 0.3 parts by mass of triethanolamine as component (D)
  • a positive resist composition was prepared in the same manner as in Example 1 except that 1250 parts by mass of a mixed solvent of PGMEA and ethyl lactate (mass ratio 6: 4) was used as an agent, and the cation part (B) component ( PAG +) and anion part (PAG-) were measured for the same concentration, and the same evaluation as in Example 1 was performed, except that the amount of elution (mol Zcm 2 ) per square centimeter of the resist layer after exposure was determined. .
  • the results are shown in Table 3.
  • Example 4 immersion exposure was performed using the positive resist composition of Example 4 (the solid content concentration was changed to 3.5 mass%).
  • an organic antireflection coating composition “ARC-29” (trade name, manufactured by Brew Science Co., Ltd.) was applied onto a silicon wafer using a spinner, and baked on a hot plate at 215 ° C. for 60 seconds. By drying, an organic antireflection film having a thickness of 77 nm was formed.
  • the positive resist composition obtained above is applied onto the antireflection film using a spinner, pre-beta for 60 seconds at 125 ° C on a hot plate, and dried to prevent reflection. A resist film having a thickness of lOOnm was formed on the film.
  • immersion two-beam interference exposure was performed using a two-beam interference exposure machine LEIES193-1 (manufactured by Nikon) using a prism, water, and two beam interferences of 193 nm.
  • PE B treatment was subjected to PE B treatment at 115 ° C. for 60 seconds, and further developed at 23 ° C. with an alkaline developer for 60 seconds.
  • alkali developing solution 2.38 wt 0/0 tetramethylammonium - using Umuhidorokishido solution.
  • Example 5 Immersion exposure was performed in the same manner as in Example 5 except that PA B was changed to 115 ° C using the positive resist composition of Comparative Example 5 (the solid content concentration was changed to 3.5% by mass). went.
  • the resist composition of Example 4 in which the amount eluted to the immersion medium was reduced was able to form a fine pattern of 45 nm and was excellent in shape.
  • the resist composition of Comparative Example 5 in which the amount of eluate in the immersion medium was larger than that in Example 4 although a fine pattern of 45 nm was formed, the rectangularity was not satisfactory.
  • the present invention can be applied to a resist composition used in a resist pattern forming method including an immersion lithography (immersion exposure) step, and a resist pattern forming method using the resist composition.

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Abstract

Composition pour enduit protecteur contenant un ingrédient générateur d’acide (B) qui est soit un générateur d’acide du type sel d’onium (B1) représenté par la formule générale suivante (b-1) (R11 à R13 représentant chacun indépendamment un groupe aryle ou un groupe alkyle, sachant qu’au moins un groupe de R11 à R13 représente un groupe aryle oú au moins un atome d’hydrogène a été remplacé par un groupe alkyle ; et Z- représentantun anion) ou un générateur d’acide de type sel d’onium (B2) comportant un anion contenant un groupe cyclique. [Formule chimique 1] (b-1)
PCT/JP2005/011737 2004-07-23 2005-06-27 Composition pour enduit protecteur et procédé de formation du motif de l’enduit protecteur WO2006008914A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2007138873A1 (fr) * 2006-05-29 2007-12-06 Tokyo Ohka Kogyo Co., Ltd. Composition de rÉsine photosensible pour exposition par immersion, et procÉdÉ de formation d'un motif de rÉsine photosensible

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JP5100115B2 (ja) * 2006-03-16 2012-12-19 東洋合成工業株式会社 スルホニウム塩及び酸発生剤
JP2008120700A (ja) * 2006-11-08 2008-05-29 San Apro Kk スルホニウム塩
EP1970760B1 (fr) 2007-03-14 2012-12-26 FUJIFILM Corporation Composition d'une réserve positive contenant une résine pour rendre hydrophobe la surface de la réserve, son procédé de production
JP5186255B2 (ja) 2007-03-20 2013-04-17 富士フイルム株式会社 レジスト表面疎水化用樹脂、その製造方法及び該樹脂を含有するポジ型レジスト組成物
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